Grease



unease Tor-stein Hasselstrom, Savannah, Ga., assignor to Gd: ALaboratories, Inc., Savannah, 6a., a corpoi-ation of Georgia.

No Drawing. Original application September 29,

1937, Serial No. 166,443.

Divided and this application December 2, 1939, Serial No. 307,281

3 Claims.

This invention relates to an improved grease and more particularly to agrease containing a non-crystalline resin product as a setting agent.

Broadly speaking, the grease prepared in accordance with my inventioncontains as the setting agent the crude, non-crystalline, brownishinsoluble product obtained by treating a mixture of dehydrogenated andhydrogenated rosin with concentrated sulfuric acid and removing thesulfonic acid by aqueous extraction.

As a suitable mixture of dehydrogenated and hydrogenated rosin I may usethe resin known to the trade as Hyex resin and prepared in accordancewith the process disclosed in United States Patent No. 2,154,629 ofApril 18, 1939, to Edwin E. Littmann entitled Process for the treatmentof abietyl compounds and products produced thereby.

Said Patent No. 2,154,629 discloses the treatment of compoundscontaining the hydrocarbon nucleus of abietic acid so as to decreasetheir apparent unsaturated character, and possibly increase theirmelting points and improve their color, and also relates to the treatedproducts so formed. Said treatment comprises contacting the abietylcompound with a catalyst of the type hereinafter described, in a. manneradapted to exclude the possibility of reaction between the abietylcompound and any other material. As a result of such treatment, a changein the chemical and physical properties of the abietyl compound,believed to be due to a simultaneous dehydrogenation and hydrogenationby the heating of the abietyl compound in the presence of thehydrogenation catalyst only, e. g. palladium takes place, and theresulting product will be found to have a greatly decreased apparentcolor.

The catalysts which may be used in efiecting this-change or intraorinter-molecular rearrangement are those which catalyze the hydrogenationof unsaturated organic compounds, for example, any of the nickel,platinum, palladium or copper chromite catalysts used in such hydrogenation. Preferably, a palladium catalyst will be employed in themethod according to this invention, for example, a catalyst comprising40% by weight of palladium supported on fibrous asbestos.

Desirably, the abietyl compound and the catalyst will be brought intocontact at an elevated,

temperature, in order' that a practical reaction rate may be obtained,but the use of an elevated temperature is not necessary for theaccomplishment of the desired results. The optimum temperature range forthe most satisfactory results is from about 150 C. to about 250 C. Sincethorough contact between catalyst and abietyl compound can best beobtained when the abietyl compound is in liquid or vapor phase, theabietyl compound, when not a liquid at the temperature employed, will beheated to render it liquid.

It is essential that the treatment of the abietyl compound be carriedout in such a manner that no reaction can occur between the abietylcompound and any other material. No added hydrogen is present during thetreatment. While the treatment may be carried out in the presence ofair, it is preferable to treat the abietyl compound in an atmosphere ofmore inert gas, for example, carbon dioxide, nitrogen, etc.

The following table shows comparative values of various chemicalconstants for treated and untreated abietyl compounds:

"I" rosin, before 1" rosin, after treatment treatment Thiocyanato number10-14. Melting goint, drop -90.

method 1 Color Slightly bleached. Saponiflcation number 16717l.

Oxygen absorption. percent of total absorbed by 2 double bonds .peroent'sulfonation by treatment by concentrated sulfuric acid of wood or gumrosin which has been simultaneously dehydrogenated and hydrogenated byheating in the presence of a hydrogenation catalyst, e. g. palladium, inaccordance with the process disclosed in Patent No. 2,154,629, and

if desired sulfonation of the resin dissolved ina solvent therefor whichis unattached or attacked by the sulfuric acid, e. g. carbontetrachloride, liquid sulfur dioxide, petroleum distillate, orunsaturated hydrocarbons and/or alcohols of the aliphatic, alicycllcand/or aromatic type.

As sulfonating agent-I preferably employ sulfuric acid of specificgravity about 1.8-4, although I may employ somewhat lower strengths ofsula brownish,

furic acid or somewhat higher strengths, even to fuming sulfuric acid orsulfur trioxide, but at the slight disadvantage of reduced yields ofmono Example I As an example of the carrying out of my proc-' ess, 100g. of the Hyex resin described above were finely pulverized and. addedgradually to 200 cc, of sulfuric acid of specific gravity 1.84 at atemperature of 10 C. with vigorous stirring. The temperature of themixture rose to 37 C., but there was no evolution of sulfur dioxide.Sulfonation was complete in 45 minutes, and the temperature dropped to 50., due to the surrounding ice bath used. The mixture was then pouredinto ice and the nearly colorless precipitate collected, washed withcold water until the washings clouded when mixed with the originalmother liquor. The washed precipitate was extracted once with boilingwater. There remained insoluble precipitate. The hot aqueous extract, oncooling, separated the sulfonic acid, having a melting point of 221-4 C;(with decomposition) or when recrystallized from glacial acetic acidhaving a melting point of 223-4 C. (with decomposition), [a]D=+71.72,

in a yield of 50 g. The yield of the brownish, insoluble product was 47g. This insoluble product may be used as a grease-setting agent, or,after removal of acid bodies by digestion with aqueous alkali, andcrystallization of the residue from acetone, yields a solid melting atabout 131.5 C. to 132 C. From the alkaline extracts of the brownish,insoluble product, an additional 10-20% or more of Hyex sulfonic acidcan be recovered by acidification. The non-crystalline material,remaining after the removal of these crystalline constituents, I havefound to be useful, after refining, e. g. by fractional distillation, asa superior rosin oilin the manufacture of printers ink, plasticizers,and the like.

Example II In a further example of the carrying out of my invention, 10g. of the Hyex resin acid obtained by fractional crystallization of Hyexresin, and having a melting point of about 156-158 C. and an opticalrotation [aln of about +43.83, was sulfonated at 10 to 15 C.'with 75 cc.of sulfuric acid in a period of 30 minutes, with vigorous stirring. Thepale orange solution resulting was poured into ice water, theprecipitate collected, washed with cold water, extracted twice withboiling water, leaving about 2 g. of insoluble material. The combinedaqueous extracts, on acidification by ,10 cc. of concentratedhydrochloric acid, precipitated 7.2 g. of asulfonic acid melting at220-3 C. (with decomposition) [a]D=+61.33 recrystallized from glacialacetic acid, melting at 223-224.5 C. (with decomposition).

Example III In a further example of the carrying out of my invention, g.of distilled Hyex resin, previously described, was dissolved in 100"cc.of carbon tetrachloride and sulfonated at 30 C.- 35 C. by 70 cc. of 95%sulfuric acid, the acid being added gradually with vigorous stirringduring a period of 45 minutes. The mixture was then pouredinto 2 litersof water, the mass re fluxed for about 10 minutes, and the two layersseparated while still warm. The carbon tetrachloride layer was againextracted with water by refluxing. The yield of sulfonic acid obtainedfromthe aqueous extracts was 35%. Evaporation of the carbontetrachloride layers left alight colored resin similar to the rawmaterial treated.

My sulfonic acid product will be found variously adaptable to uses as animproved detergent and wetting out agent, e. g. in the scouring oftextiles, as a soap assistant, etc.

I may prepare the neutral or acid alkali or alkaline earth, or organicbase, e. g. ethanolamine, salts of my sulfonic acid product, and suchalso are variously adaptable to uses as improved detergents and wettingout agents.

The non-crystalline, brownish material separated from the sulfonic acid,as shown, for example, in Examples I and II, I have found useful as agrease-setting and/or emulsifying agent, e. g, in the manufacture of cupgrease, solid oils, and the like.

Example IV As an example of carrying out my process of making a. coldset grease, the non-crystalline, brownish material separated from thesulfonic acid, as shown, for example, in Examples I and II, was dried toabout constant weight. Seven and one-half grams of this dried materialwas dissolved at about C. in 22.5 g. of mineral oil of about 100 sec.viscosity (Saybolt) at 100 F., after cooling, the solution wassaponified at room temperature, of about 25 C., with 70 g. of mineraloil, 100 sec. viscosity (Saybolt) at 100 F., containing 25% of suspendedcalcium hydroxide and stirred for about 10 sec. to about 2 minutes toform a grease.

This application is a division of my application, Serial No. 166,443 forDetergent and wetting agent and process of producing the same, filed byme September 29, 1937, which is in turn a continuation-in-part of myapplication, Serial No. 70,672, filed by me March 24, 1936, and nowissued as Patent 2,121,033 of June 21, 1938.

What I claim and desire to protect by Letters Patent is:

1. A grease including as a setting agent the crude, non-crystalline,brownish insoluble product obtained by treating a mixture ofdehydrogenated and hydrogenated rosin with concen-- trated sulfuric acidunder conditions which promote sulfonation and removing the sulfonicacid by aqueous extraction.

2. A grease including as a setting agent the crude, non-crystalline,brownish insoluble product obtained by treating a resin prepared byheattreating rosin in the presence of a hyrogenation catalyst and in theabsence of added substances capable of reducing the degree ofunsaturation of the rosin, with concentrated sulfuric acid underconditions which promote sulfonation and removing the sulfonic acid byaqueous extraction.

3. A cup grease including mineral oil and as a setting agent the crude,non-crystalline, brownish insoluble product obtained by treating a resinprepared by heat-treating rosin. in the presence of a hydrogenationcatalyst and in the absence of added substances capable of reducing thedegree of unsaturation of the rosin, with concentrated sulfuric acidunder conditions which promote sulfonation and removing the sulfonicacid by aqueous extraction.

'- TORSTEN HASSELSTROM.

